CN113563858A - Surfactant composition for oil displacement of high-temperature and high-salinity oil reservoir - Google Patents
Surfactant composition for oil displacement of high-temperature and high-salinity oil reservoir Download PDFInfo
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Abstract
The invention provides a surfactant composition for a high-temperature and high-salinity oil reservoir oil displacement agent, which comprises a main agent, a synergist and a cosolvent. The oil displacement agent has good interfacial activity, can further reduce the oil-water interfacial tension, has strong solubilization and emulsification effects, interaction, synergy, uniform and stable system, continuous and stable oil displacement performance, and can effectively improve the oil displacement efficiency.
Description
Technical Field
The invention belongs to the technical field of chemical flooding oil extraction, and particularly relates to a surfactant composition for oil displacement of a high-temperature high-salinity reservoir and application thereof.
Background
Along with the gradual development of oil fields, the problems of low production speed and low production degree of high-temperature and high-salinity oil reservoirs are increasingly highlighted, and the development of a temperature-resistant and salt-resistant surfactant system is favorable for improving the crude oil recovery rate. The chemical compound oil displacement technology can greatly improve the recovery ratio of crude oil, has achieved obvious oil increasing effect in Daqing oil fields in China, and increases more than 3300 million tons of crude oil in cumulative yield increase since application in mine fields in 2014. The chemical compound flooding technology comprises ternary compound flooding, which is a strong base ternary flooding system consisting of polymer, surfactant and sodium hydroxide and a weak base ternary flooding system consisting of polymer, surfactant and sodium carbonate; and an alkali-free binary oil displacement system consisting of two chemical agents, namely a polymer and a surfactant. The composite oil displacement mechanism mainly comprises the steps of improving the system viscosity, increasing swept volume and mainly contributing to polymers; and secondly, the oil-water interfacial tension is reduced, the emulsification is generated, the oil displacement efficiency is improved, and higher requirements are provided for further reducing the interfacial tension of the surfactant.
In the ternary combination flooding, the addition of alkali can improve the dispersibility of fine particles such as clay, minerals and the like in a stratum and accelerate the migration of the fine particles, so that the pore throats of rocks are blocked, the stratum structure is damaged, secondary damage to an oil reservoir can be caused, in addition, the phenomena of pipe column corrosion, scaling of a production well, pump sticking, rod breaking and serious emulsification of crude oil can be caused, and great burden is brought to the subsequent demulsification and dehydration process. The alkali three-element combination flooding has started to be limited in the oil field, and the use of alkali brings more harm to high-temperature and high-salt oil reservoirs. The gradual progress of the ternary combination flooding to the alkali-free state is an inevitable requirement of technical progress and is a development direction of a combination flooding technology, an alkali-free binary flooding system hardly has damage to stratums, but no report of large-scale mine field application exists at present.
The prior alkali-free binary composite surfactant for oil displacement generally has the advantages of wider ultra-low interfacial tension range and good stability. But the general defects are that the system has poor temperature and salt resistance, the enhanced recovery ratio is relatively low, and even the oil reservoir with the temperature of 80 ℃ or above and high mineralization degree (more than or equal to 600mg/L) of calcium and magnesium ions can not meet the application requirements completely. For a harsh high-temperature and high-salinity oil reservoir, if an alkali-free binary composite oil displacement technology is adopted, the improvement of the stability, temperature resistance and salt resistance of the surfactant for oil displacement is particularly important.
Disclosure of Invention
In order to solve the problems, the invention provides a surfactant composition for a high-temperature high-salt oil reservoir oil displacement agent, wherein fatty amine polyoxypropylene polyoxyethylene ether sulfonate serving as a main agent has good interfacial activity and can further reduce the oil-water interfacial tension; in addition, quaternary ammonium salt is added as a synergist, so that a supermolecular structure with higher interfacial activity can be formed with the main agent, and the effect of stabilizing the performance of the composition is achieved; the polyglycerol ether containing polyoxypropylene ether and/or polyoxyethylene ether chain segments is used as a cosolvent, has strong solubilization and emulsification effects, can fuse a main agent and a synergist, enables the main agent and the synergist to interact and synergize synergistically, enables organic components and water to be better dissolved mutually, and is uniform and stable in system, so that the invention is completed.
The invention aims to provide a surfactant composition for a high-temperature high-salinity reservoir oil displacement agent, which comprises a main agent and a synergist.
The main agent is fatty amine polyoxypropylene polyoxyethylene ether sulfonate, and a polyoxypropylene chain segment and a polyoxyethylene chain segment are introduced through fatty amine etherification;
the synergist is selected from quaternary ammonium salts, preferably one or more of alkyl trimethyl quaternary ammonium salts, Gemini quaternary ammonium salts and quaternary ammonium salts containing polyoxyethylene ether blocks, and more preferably one or more of fatty alcohol polyoxyethylene glycidyl ether quaternary ammonium salts.
Preferably, the composition further comprises a cosolvent, wherein the cosolvent is one or more selected from fatty alcohol polyoxyethylene polyglyceryl ether, fatty amine polyoxyethylene polyglyceryl ether, fatty alcohol polyoxypropylene polyoxyethylene polyglyceryl ether and fatty amine polyoxypropylene polyoxyethylene polyglyceryl ether.
The cosolvent is prepared by carrying out substitution reaction on polyether and halogenated epoxypropane to obtain a glycidyl ether intermediate containing epoxy bonds, and then carrying out ring-opening reaction on the glycidyl ether intermediate and polyglycerol.
The fatty amine polyoxypropylene polyoxyethylene ether sulfonate is prepared by etherifying, alkenylating and sulfonating fatty amine.
The fatty alcohol-polyoxyethylene ether reacts with halogenated propylene oxide in an alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst to obtain fatty alcohol-polyoxyethylene glycidyl ether, and trimethylamine and concentrated acid are added to react to obtain the fatty alcohol-polyoxyethylene glycidyl ether quaternary ammonium salt.
The main agent is fatty amine polyoxypropylene polyoxyethylene ether sulfonate, which has the following structure:
wherein R is alkyl or substituted aryl; m + n is more than or equal to 2 and less than or equal to 20, m is 2-20, and n is 2-20; i is 2-8; m, n and i are integers.
The fatty alcohol polyoxyethylene glycidyl ether quaternary ammonium salt has the following structure:
R0is alkyl or substituted aromatic; p is 2-20; p is an integer.
The cosolvent has the following structure:
wherein R is1Is alkyl or substituted aromatic; e is nitrogen or oxygen; a + b is more than or equal to 2 and less than or equal to 20; a is 0 to 20; b is 1 to 20; c is 2, 3 or 4; a. b and c are integers.
The second aspect of the invention aims to provide the application of the surfactant composition for the high-temperature high-salinity reservoir oil displacement agent, wherein the composition is used for crude oil displacement with reservoir temperature higher than 70 ℃, preferably higher than 80 ℃ and mineralization higher than 15000 mg/L.
The surfactant composition for the oil displacement agent of the high-temperature and high-salinity oil reservoir provided by the invention has the following beneficial effects:
(1) the invention uses fatty amine polyoxypropylene polyoxyethylene ether sulfonate as a main agent which has good interfacial activity and can further reduce the oil-water interfacial tension.
(2) The quaternary ammonium salt is added as a synergist, can be synergized with the main agent, and particularly can form a supermolecular structure with higher interfacial activity with the main agent to play a role in stabilizing the performance of the composition.
(3) The polyglycerol ether containing polyoxypropylene ether and/or polyoxyethylene ether chain segments is used as a cosolvent, has a strong solubilizing and emulsifying effect, can fuse a main agent and a synergist, enables the main agent and the synergist to interact and synergize synergistically, enables organic components and water to be better dissolved mutually, is uniform and stable in system, and effectively improves the oil displacement rate.
Drawings
FIG. 1 is an appearance diagram showing the results of emulsification of an oil-displacing agent I, a comparative sample I and a comparative sample II in simulated water and crude oil of the same volume in Experimental example 2 of the present invention;
FIG. 2 is a graph showing the oil-water interfacial tension of solutions of oil-displacing agent I, comparative sample II and oil-displacing agent III according to the surfactant concentration in Experimental example 3 of the present invention.
Detailed Description
The present invention will now be described in detail by way of specific embodiments, and features and advantages of the present invention will become more apparent and apparent from the following description.
The surfactant composition for the oil displacement agent of the high-temperature and high-salt oil reservoir provided by the invention utilizes the performance characteristics of the main agent, the synergist and the cosolvent, so that the supermolecule effect is realized in the oil displacement agent, the interfacial activity is enhanced, the interfacial tension of the oil displacement agent is effectively reduced, and meanwhile, the stability, temperature resistance and salt tolerance of the whole oil displacement system are improved by adding the synergist and the cosolvent, so that the performance of the oil displacement agent is further improved, and the oil displacement rate is improved.
The invention provides a surfactant composition for a high-temperature and high-salinity oil reservoir oil displacement agent, which comprises a main agent and a synergist.
The main agent is fatty amine polyoxypropylene polyoxyethylene ether sulfonate, and a polyoxypropylene chain segment and a polyoxyethylene chain segment are introduced through fatty amine etherification, so that the lipophilicity, the water solubility and the salt resistance of the main agent are improved. It has the following structure:
wherein R is alkyl or substituted aromatic, preferably C10-C25Alkyl or C10-C25Alkylphenyl, more preferably C12-C22Such as dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl.
m + n is not less than 2 and not more than 20, m is 2 to 20, n is 2 to 20, preferably m is 2 to 16, n is 2 to 16, more preferably m is 5 to 10, and n is 5 to 10. i is 2 to 8, preferably 2 to 6, more preferably 2 to 4, such as 3. m, n and i are integers.
In the invention, when R group in the main agent fatty amine polyoxypropylene polyoxyethylene ether sulfonate is alkyl and substituted aryl, the interface performance of the oil displacement agent can be improved, and the alkyl is better, so that the pollution to oil displacement water and stratum is reduced, and the environmental burden is reduced.
m and n are the numbers of Propoxy (PO) and Ethoxy (EO) respectively, wherein, the extension of a polyoxypropylene (PPO) chain segment in an oil phase ensures the lipophilicity of the molecule and does not destroy the water solubility of the molecule, and the Polyoxyethylene (PEO) chain segment enables the surfactant molecule to have nonionic property and improves the water solubility and the water resistance. A large number of experiments show that in the application process, the lengths of the PPO and PEO chain segments embedded in the invention reduce the interfacial tension and the salt resistance, the solubilization capacity is strong, the spatial structure of molecules is extended, the adsorption retention effect is effectively weakened, the emulsification capacity is enhanced, and the improvement of the crude oil recovery ratio is facilitated.
The fatty amine polyoxypropylene polyoxyethylene ether sulfonate is prepared by etherifying, alkenylating and sulfonating fatty amine.
The fatty amine is a primary amine selected from alkylamine or substituted arylamine, preferably C10-C25Of alkylamine or C10-C25Alkylphenylamine, more preferably C12-C22Such as 1-dodecylamine, 1-tetradecylamine, 1-hexadecylamine, 1-octadecylamine, docosane-1-amine.
The etherification is carried out with propylene oxide firstly and then with ethylene oxide to obtain the fatty amine polyoxypropylene polyoxyethylene ether. The reaction is carried out under the condition of protective gas, such as under the protection of nitrogen, and then the reaction is carried out with propylene oxide and ethylene oxide.
Preferably, the etherification reaction is carried out in the presence of a catalyst selected from organic or inorganic bases, preferably alkali metal hydroxides, such as KOH, NaOH.
The molar ratio of the aliphatic amine to the propylene oxide is 1 (4-40), preferably 1 (4-32), and more preferably 1 (5-20). The molar ratio of the aliphatic amine to the ethylene oxide is 1 (4-40), preferably 1 (4-32), and more preferably 1 (5-20).
The etherification reaction temperature is 100-180 ℃, and preferably 120-160 ℃.
And the alkenylation is carried out on fatty amine polyoxypropylene polyoxyethylene ether and halogenated olefin. The halogenated olefin is selected from halogenated mono-olefin, preferably containing C2-C8More preferably 3-chloropropene.
In the olefination reaction, alkali metal hydride is added into fatty amine polyoxypropylene polyoxyethylene ether for reaction, after deoxygenation and dehydration, halogenated olefin is added for reaction, and the olefination fatty amine polyoxypropylene polyoxyethylene ether is obtained. For example:
wherein j is the number of methylene groups in the halogenated olefin and j is an integer.
The molar ratio of the fatty amine polyoxypropylene polyoxyethylene ether to the halogenated olefin is 1 (2.0-5.5), preferably 1 (2.2-6.5), and more preferably 1 (2.5-3.5). The etherification reaction temperature is 60-110 ℃, and preferably 70-90 ℃.
And reacting the sulfonated fatty amine polyoxypropylene polyoxyethylene ether with a sulfonating agent to obtain the fatty amine polyoxypropylene polyoxyethylene ether sulfonate. The sulfonating agent is selected from bisulfite and/or sulfite, preferably sodium bisulfite and sodium sulfite, and the molar ratio of the bisulfite and the sodium sulfite is 1 (0.8-3), preferably 1 (1.0-1.5).
The sulfonation reaction is carried out in the presence of a catalyst nitrate, and the addition amount of the nitrate is 10-40% of the molar amount of the alkenyl fatty amine polyoxypropylene polyoxyethylene ether. The reaction is carried out in a solvent, wherein the solvent is selected from one or more of water and alcohol solvents, preferably one or more of water, methanol and ethanol, and more preferably water and ethanol. The sulfonation reaction temperature is 60-100 ℃, and preferably 70-90 ℃.
The synergist is selected from quaternary ammonium salts, preferably from alkyltrimethyl quaternary ammonium salts, such as dodecyltrimethyl ammonium chloride, tetradecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, dodecyltrimethyl ammonium bromide, tetradecyltrimethyl ammonium bromide, hexadecyltrimethyl ammonium bromide, octadecyltrimethyl ammonium bromide, Gemini quaternary ammonium salts, such as ethylpropylbutylbis (dodecyldimethyl ammonium chloride), ethylpropylbutylbis (tetradecyldimethyl ammonium chloride), ethylpropylbutylbis (hexadecyldimethyl ammonium chloride), ethylpropylbutylbis (octadecyldimethyl ammonium chloride), ethylpropylbutylbis (dodecyldimethyl ammonium bromide), ethylpropylbutylbis (tetradecyldimethyl ammonium bromide), Ethyl/propyl/butyl-ethylene bis (hexadecyl dimethyl ammonium bromide), ethyl/propyl/butyl-ethylene bis (octadecyl dimethyl ammonium bromide) and one or more of quaternary ammonium salts containing polyoxyethylene ether blocks, preferably one or more of fatty alcohol polyoxyethylene glycidyl ether quaternary ammonium salts.
The fatty alcohol polyoxyethylene based glycidyl ether quaternary ammonium salt has the following structure:
R0is an alkyl or substituted aromatic group, preferably C10-C25Alkyl or C10-C25Alkylphenyl, more preferably C12-C22Such as dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl. p is 2 to 20, preferably 2 to 16, and more preferably 5 to 9. p is an integer.
In the invention, the synergist and the main agent interact to form a supermolecule system, thereby enhancing the interfacial activity of the whole oil displacement system. R in synergist0On one hand, the environment friendliness of the oil displacement agent can be influenced, and on the other hand, R0The salt resistance and the hydrophilic-lipophilic balance of the composite material can be influenced by the number of EO, more importantly, the composite material can influence the formation of the supermolecule action of the synergist and the main agent, and a large number of experiments can determine that when the p value is 2-20, an effective supermolecule system can be formed between the synergist and the main agent, and when the p value is 5-9, the system stability is good, and meanwhile, the temperature resistance and the salt resistance can also be improved.
According to the invention, fatty alcohol-polyoxyethylene ether reacts with halogenated propylene oxide in an alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst to obtain fatty alcohol-polyoxyethylene glycidyl ether, and trimethylamine and concentrated acid are added to react to obtain the fatty alcohol-polyoxyethylene glycidyl ether quaternary ammonium salt.
For example:
the concentrated acid is selected from concentrated hydrochloric acid or concentrated sulfuric acid, preferably concentrated hydrochloric acid.
In the invention, the mass ratio of the main agent to the synergist is 100 (1-16), preferably 100 (1.5-8), and more preferably 100 (2-5).
In a preferred embodiment of the present invention, the surfactant composition for a high-temperature and high-salt reservoir oil displacing agent further comprises a cosolvent, wherein the cosolvent is selected from one or more of fatty alcohol polyoxyethylene polyglycerol ether, fatty amine polyoxyethylene polyglycerol ether, fatty alcohol polyoxypropylene polyoxyethylene polyglycerol ether and fatty amine polyoxypropylene polyoxyethylene polyglycerol ether, and is preferably one or more of fatty amine polyoxypropylene polyoxyethylene polyglycerol ether.
Preferably, the co-solvent has the following structure:
wherein the content of the first and second substances,
R1is an alkyl or substituted aromatic group, preferably C10-C25Alkyl or C10-C25Alkylphenyl, more preferably C12-C22Such as dodecyl, tetradecyl, hexadecyl, octadecyl, docosyl.
E is nitrogen or oxygen, preferably nitrogen.
a + b is not less than 2 and not more than 20. a is 0 to 20, preferably 2 to 16, and more preferably 5 to 8; b is 1 to 20, preferably 2 to 16, and more preferably 5 to 8. c is 2, 3 or 4, preferably 2. a. b and c are integers.
The cosolvent can promote the dispersion of the main agent in the solution and improve the temperature resistance and salt resistance of the oil displacement agent.
The cosolvent is prepared by carrying out substitution reaction on polyether and halogenated epoxypropane to obtain a glycidyl ether intermediate containing epoxy bonds, and then carrying out ring-opening reaction on the glycidyl ether intermediate and polyglycerol. The cosolvent is prepared by the following method:
step 1, preparing polyglycerol.
The polyglycerol was prepared according to the classical method. Mixing glycerol and sodium hydroxide, heating to 250 ℃ in a nitrogen environment, and preparing polyglycerol with polymerization degrees of 2, 3 and 4 respectively according to the refractive index.
And 2, adding halogenated epoxypropane into a solvent containing polyether, and heating for reaction to obtain a glycidyl ether intermediate containing an epoxy chain segment.
The polyether is selected from one or more of fatty alcohol polyoxyethylene ether, fatty amine polyoxyethylene ether, fatty alcohol polyoxypropylene polyoxyethylene ether and fatty amine polyoxypropylene polyoxyethylene ether.
Adding polyether into an alkaline aqueous solution, adding a phase transfer catalyst, slowly dropwise adding epoxy chloropropane under a heating condition for reaction, standing for layering after the reaction is finished, and separating a lower layer to obtain a glycidyl ether intermediate containing an epoxy chain segment.
The molar ratio of the polyether to the epichlorohydrin is 1 (1.5-4.5), preferably 1 (1.8-3.5), and more preferably 1 (2.1-3).
The molar ratio of the phase transfer catalyst to the polyether is (0.01-0.08):1, preferably (0.02-0.05): 1.
The reaction temperature is 40-65 ℃, preferably 45-60 ℃.
And 3, adding the glycidyl ether intermediate containing the epoxy chain segment into the polyglycerol, and carrying out heat preservation reaction to obtain the cosolvent.
Firstly, adding polyglycerol into sodium hydroxide alcoholic solution, stirring for reaction, removing ethanol and a small amount of water after the reaction is finished, adding glycidyl ether intermediate containing epoxy bonds, and continuously vacuumizing, heating and preserving heat for reaction. After the reaction is finished, washing with alcohol, filtering and drying to obtain the cosolvent.
The mass concentration of the sodium hydroxide alcoholic solution is 4-15%, preferably 6-12%, and more preferably 8-10%. The alcohol is one or more of ethanol, propanol, butanol and isopropanol, preferably ethanol or propanol, more preferably ethanol.
The molar ratio of the glycidyl ether intermediate containing an epoxy bond to the polyglycerol is 1 (1.5-5), preferably 1 (1.8-4), and more preferably 1 (2.0-3.0).
The reaction temperature of the glycidyl ether intermediate containing an epoxy bond and the polyglycerol is 100-180 ℃, preferably 120-170 ℃, and more preferably 140-160 ℃.
In the invention, the mass ratio of the main agent to the cosolvent is 100 (2-25), preferably 100 (5-20), and more preferably 100 (8-15).
In the invention, the surfactant composition for the oil displacement agent of the high-temperature and high-salinity oil reservoir is used in a solvent. The solvent is selected from one or more of alcohol solvents and ether solvents, more preferably one or more of isopropanol, n-propanol, n-butanol, n-pentanol, isoamyl alcohol, ethylene glycol monobutyl ether, propylene glycol monobutyl ether, monoethylene glycol, diethylene glycol and triethylene glycol, and more preferably one or more of ethylene glycol monobutyl ether, propylene glycol monobutyl ether and isopropanol.
The solvent also includes water selected from distilled water, deionized water, tap water, mineral water or groundwater.
The mass-volume ratio of the surfactant composition to the solvent for the oil displacement agent for the high-temperature and high-salinity oil reservoir is (1-20) g (100-150) mL, and preferably (2-15) g (100-150) mL.
The surfactant composition for oil displacement of the high-temperature high-salt oil reservoir takes a negative nonionic surfactant, namely tertiary amine polyoxypropylene polyoxyethylene ether sulfonate, as a main agent, takes a quaternary ammonium salt as a synergist, particularly takes fatty alcohol polyoxyethylene glycidyl ether quaternary ammonium salt as a synergist, takes polyglycerol ether containing polyoxypropylene ether and/or polyoxyethylene ether chain segments as a cosolvent, and is matched for use to realize synergistic interaction, so that the surfactant composition has excellent interfacial activity, the oil-water ultralow interfacial tension can be further effectively reduced, a supermolecular structure with high interfacial activity can be formed, the system is uniform and stable, the surfactant composition with stable and lasting performance can be obtained, particularly, the oil displacement agent is prepared, and the surfactant composition has excellent and stable performance and can effectively improve the oil displacement efficiency.
Examples
Example 1
Adding 2mol of 1-dodecylamine into a reaction kettle, adding 100mL of 10mol/L KOH solution, vacuumizing the reaction kettle, introducing nitrogen, circulating for 3 times to ensure the vacuum environment, heating to 160 ℃, adding 20mol of propylene oxide into the reaction kettle, and reacting until the system pressure is not changed. Vacuumizing the reaction kettle, introducing nitrogen, circulating for 3 times to ensure the vacuum environment, adding 20mol of ethylene oxide, and reacting at 160 ℃ until the system pressure is not changed any more to obtain the dodecyl amine polyoxypropylene polyoxyethylene ether, wherein the reaction molar yield is more than 95%.
Adding 1.5mol of dodecylamine polyoxypropylene polyoxyethylene ether and 1.5mol of sodium hydroxide solid into a reaction kettle, introducing nitrogen to remove oxygen and dehydrate, stirring and reacting at 100 ℃ for 2.5h, and cooling to room temperature. Heating to 80 ℃, slowly dropwise adding 3.8mol of 3-chloropropene, stirring and reacting for 8h, washing with hot deionized water, adding sodium hydroxide to adjust the pH value to be neutral, standing and layering, taking supernatant, and performing rotary evaporation to remove unreacted 3-chloropropene to obtain allyl dodecyl amine polyoxypropylene polyoxyethylene ether, wherein the reaction molar yield is more than 85%.
1mol of allyl dodecyl amine polyoxypropylene polyoxyethylene ether, 500mL of deionized water and 30g of sodium nitrate are added into a reaction kettle. Dissolving 0.6mol of sodium bisulfite and 0.6mol of sodium sulfite in 500mL of deionized water, slowly adding the mixture into a reaction kettle, stirring and reacting at 80 ℃ for 12 hours, extracting with petroleum ether after the reaction is finished, and removing the solvent by rotary evaporation to obtain the dodecylamine polyoxypropylene polyoxyethylene ether sulfonate.
Example 2
Behenylamine polyoxypropylene polyoxyethylene ether sulfonate was prepared as in example 1, except that: the 1-dodecylamine is replaced with an equimolar amount of docosane-1-amine.
Example 3
Adding 2mol of lauryl polyoxyethylene ether (AEO-9), 2mol of NaOH solid and 0.04mol of tetrabutylammonium bromide (TBAB) into a reaction kettle, adding 600mL of normal hexane, stirring for dissolving, simultaneously dropwise adding 2.2mol of epichlorohydrin, heating to 50 ℃, reacting for 10 hours under strong stirring, stopping stirring, standing for layering. And distilling the upper layer under reduced pressure to evaporate unreacted epoxy chloropropane to obtain lauryl alcohol polyoxyethylene glycidyl ether with the molar yield of 97%.
1mol of dodecanol polyoxyethylene glycidyl ether, 200mL of a 33% trimethylamine aqueous solution and 300mL of absolute ethanol were added to a reaction kettle, and stirred at room temperature to dissolve the mixture. Adding 100mL of concentrated HCl (mass fraction of 37%) into the reaction solution to neutralize to neutrality, heating to 85 ℃, refluxing for reaction for 3H, evaporating ethanol and water, separating by using strong acid cation exchange resin (AMBERLITE IR-120(H) ion exchange resin), and vacuum drying to obtain the lauryl alcohol polyoxyethylene glycidyl ether quaternary ammonium salt. The molar yield was 92%.
Example 4
A quaternary ammonium salt of behenyl polyoxyethylene glycidyl ether was prepared as in example 3, except that: the lauryl polyoxyethylene ether was replaced with an equimolar amount of behenyl polyoxyethylene ether.
Example 5
9mol of glycerol and 1.5mol of sodium hydroxide are added into a reaction kettle, nitrogen is introduced, the temperature is slowly raised to 250 ℃, and the polyglycerol with the polymerization degree of 3 is prepared.
Adding 1mol of the dodecylamine polyoxypropylene polyoxyethylene ether prepared in the example 1, 100mL of a 5mol/L NaOH aqueous solution and 0.02mol of tetrabutylammonium bromide into a reaction kettle, stirring for dissolving, simultaneously dropwise adding 2.2mol of epoxy chloropropane, heating to 50 ℃, reacting for 10 hours under strong stirring, stopping stirring, standing for separating an upper layer, distilling out unreacted epoxy chloropropane through reduced pressure distillation to obtain a dodecylamine polyoxypropylene polyoxyethylene ether glycidyl ether intermediate, wherein the molar yield is 96%.
Respectively adding 1.6mol of polyglycerol and 160mL of 10% sodium hydroxide ethanol solution in mass fraction into a reaction kettle, heating in vacuum to remove ethanol and water in the raw materials, then adding 0.8mol of dodecylamine polyoxypropylene polyoxyethylene ether glycidyl ether intermediate, continuing to vacuumize and heat to 150 ℃, and keeping the temperature to react for 10 hours. Washing with ethanol, filtering and drying to obtain the dodecylamine polyoxypropylene polyoxyethylene polyglycerol ether with the molar yield of 85 percent.
Example 6
Docosylamine polyoxypropylene polyoxyethylene polyglyceryl ether was prepared as in example 5, with the only difference that: the dodecylamine polyoxypropylene polyoxyethylene ether was replaced with an equimolar amount of behenylamine polyoxypropylene polyoxyethylene ether.
Examples of the experiments
Experimental example 1
2.64g of dodecylamine polyoxypropylene polyoxyethylene ether sulfonate prepared in example 1 is taken as a main agent, 0.06g of lauryl alcohol polyoxyethylene glycidyl ether quaternary ammonium salt prepared in example 3 is taken as a synergist, 0.3g of dodecylamine polyoxypropylene polyoxyethylene polyglycerol ether prepared in example 5 is taken as a cosolvent, the materials are added into 15mL of isopropanol and uniformly dispersed and dissolved, deionized water is added to prepare 100g of solution, and the solution is mixed and dispersed to obtain the oil displacement agent I.
2.64g of behenylamine polyoxypropylene polyoxyethylene ether sulfonate prepared in example 2 as a main agent, 0.06g of behenyl alcohol polyoxyethylene glycidyl ether quaternary ammonium salt prepared in example 4 as a synergist, and 0.3g of behenylamine polyoxypropylene polyoxyethylene polyglycerol ether prepared in example 6 as a cosolvent were added into 15mL of isopropanol to be uniformly dispersed and dissolved, deionized water was added to prepare 100g of solution, and the solution was mixed and dispersed to obtain an oil-displacing agent II.
6g of a heavy alkylbenzene sulfonate (commercially available) and 8.6g of fatty alcohol polyoxyethylene ether sodium sulfate (AES-9) were added with deionized water to prepare 100g of solutions, and a control sample I and a control sample II were obtained.
Respectively adding 10g of oil displacement agent I, 10g of oil displacement agent II, 10g of comparison sample I and 10g of comparison sample II into 90mL of simulated water with the mineralization degree of 16945mg/L and the calcium and magnesium ions of 750mg/L, and respectively stirring uniformly. And (3) at 86 ℃ (simulating the temperature of the oil reservoir), standing for 24h, and evaluating the compatibility of the sample according to the dissolution and precipitation conditions.
Experimental results prove that in simulated water and at the oil reservoir temperature, the oil displacement agent I and the oil displacement agent II have good compatibility, no precipitate is generated after the oil displacement agent I and the oil displacement agent II are placed for 24 hours, and the heavy alkylbenzene sulfonate and the sodium fatty alcohol polyoxyethylene ether sulfate (AES-9) have precipitates of different degrees.
Experimental example 2
Respectively adding 10g of oil displacement agent I, 10g of comparison sample I and 10g of comparison sample II into 90mL of simulated water with the mineralization degree of 16945mg/L and the calcium-magnesium ion content of 750mg/L, adding crude oil with the same volume, and detecting the emulsifying capacity at 86 ℃.
Experimental results prove that under the conditions of simulated oil water and reservoir temperature, the emulsification capacity of the oil displacement agent I and the oil displacement agent II is superior to that of the conventional comparison sample I and the comparison sample II after the oil displacement agent I and the oil displacement agent II are placed for 24 hours. The appearance of the emulsification result is shown in FIG. 1.
Experimental example 3
The dodecylamine polyoxypropylene polyoxyethylene ether sulfonate prepared in example 1 was dissolved in isopropanol (the mass-to-volume ratio of dodecylamine polyoxypropylene polyoxyethylene ether sulfonate to isopropanol was 2.64g:15mL) to prepare an oil-displacing agent III.
Respectively adding the oil displacement agent I, the comparison sample II and the oil displacement agent III into hypersalinity (the mineralization is 16945mg/L, and the calcium and magnesium ions are 750mg/L) simulated water, and respectively preparing solutions with mass concentrations of 0.05%, 0.1%, 0.2% and 0.3%. The oil-water interfacial tension test was performed at 86 ℃, and the test results are shown in table 1, and the trend is shown in fig. 2.
As can be seen from Table 1, the interfacial tension of the oil-displacing agent I system is always less than 10-2mN/m is superior to other three surfactant systems. The surfactant composition for oil displacement of the high-temperature and high-salinity oil reservoir provided by the invention has extremely excellent interfacial tension performance.
TABLE 1 interfacial tension of solutions of oil-displacing agent I, control II and oil-displacing agent III
Experimental example 4
The surfactant composition for oil displacement of the high-temperature and high-salinity oil reservoir is added with water to prepare an oil displacement agent IV and an oil displacement agent V.
The surfactant composition for oil displacement of high-temperature and high-salinity oil reservoirs is prepared by dissolving the composition in isopropanol (the mass-volume ratio of the dodecyl amine polyoxypropylene polyoxyethylene ether sulfonate to the isopropanol is 2.64g:15mL), and adding water with high mineralization to prepare an oil displacement agent IV and an oil displacement agent V. (mineralization degree in hypersalinity water is 16945mg/L, calcium and magnesium ions are 750mg/L)
The concentrations of the surfactant composition for oil displacement of the high-temperature high-salinity oil reservoir in the oil displacement agent IV and the oil displacement agent V are 0.3 wt% and 0.2 wt% respectively.
And adding the heavy alkylbenzene sulfonate and the fatty alcohol-polyoxyethylene ether sodium sulfate into the high-salinity water to prepare an oil displacement agent VI and an oil displacement agent VII. In the oil displacement agent VI, the concentration of the heavy alkylbenzene sulfonate is 0.3 wt%; in the oil displacing agent VII, the concentration of the sodium alcohol ether sulphate is 0.3 wt%.
The resulting mixture was placed in a sealed ampoule at 86 ℃ and a degree of mineralization of 16945mg/L and a calcium-magnesium ion concentration of 750mg/L for 90 days, and the interfacial tension values after 30 days and after 90 days were measured, and the results are shown in Table 2.
TABLE 2 oil displacing agent interfacial tension stability results
The results in table 2 prove that the oil-displacing agent IV and the oil-displacing agent V prepared from the surfactant composition for oil displacement of high-temperature and high-salinity oil reservoirs can still reach ultralow interfacial tension after aging for 90 days under simulated water and oil reservoir temperature (86 ℃), and the oil-displacing agent IV and the oil-displacing agent V are more suitable for high-temperature and high-salinity oil reservoirs.
Experimental example 5
The oil displacement agent IV, the oil displacement agent VI and the oil displacement agent VII in the experimental example 4, and the pure polymer polyacrylamide oil displacement agent VIII (the concentration of the polyacrylamide aqueous solution is 1700mg/L) are prepared by using a natural core of a certain Russian oil field, wherein the core length is 12cm, the diameter is 3.0cm, and the water-measured permeability is 25 multiplied by 10-3μm2At a temperature of 8The displacement experiment conditions of the physical simulation oil displacement test at 6 ℃ and under the produced water conditions (the degree of mineralization is 16945mg/L, and the calcium and magnesium ions are 750mg/L) are as follows:
(1) washing oil from a natural core, drying, measuring the size length and diameter of the core, saturating and injecting water at room temperature, and measuring the porosity and the pore volume;
(2) saturating the crude oil at 86 ℃, controlling the saturation of the bound water to be 35-37%, and aging overnight;
(3) displacement experiment temperature 86 ℃, injection rate: 0.1 ml/min;
(4) after the water is driven to contain 98 percent of water, 1700mg/L polyacrylamide solution 0.1PV and 0.3PV oil-displacing agent are injected, 0.2PV 1700mg/L polyacrylamide solution is injected, and the pressure, the oil production and the water production are recorded every 5min (the polymer oil-displacing system VIII is injected with 0.6PV 1700mg/L polyacrylamide solution);
(5) and (4) performing subsequent water flooding until the water content is 100%, recording the pressure, the oil production and the water production every 10min until the oil production is not increased within 30min, stopping flooding, calculating the recovery ratio according to the liquid production and the water content of each stage, and automatically collecting the pressure by a pressure sensor in the whole experimental process.
The test results are shown in table 3.
Table 3 physical simulation oil displacement experiment result of natural rock core
The results in table 3 show that when the oil displacement agent iv of the present invention is applied to a certain oil field core and oil-water condition in russia, the recovery ratio can be further improved by more than 18.48% OOIP (0.1PV pre-slug +0.3PV oil displacement agent +0.2PV subsequent protective slug) on the basis of water displacement when the concentration is 0.3% wt (the oil-water interfacial tension is reduced to 0.0017mN/m, and the viscosity reaches 12.0mpa.s), while the oil displacement agent vi adopts a natural core with the same slug (0.1PV pre-slug +0.3PV oil displacement agent +0.2PV subsequent protective slug), the same concentration (0.3 wt% surfactant) and similar permeability, and the oil displacement agent vii adopts a surfactant with a structure similar to that of the present invention, but the chemical recovery ratio of the two oil displacement agents can only be improved by 10.22% OOIP and 11.29% OOIP compared with water displacement agent. Similarly, the same slug (0.6PV) and the concentration of 1700mg/L are adopted for the oil displacement agent VIII, but the chemical flooding recovery efficiency can be improved by 7.45 percent OOIP compared with water flooding, which shows that the oil displacement agent IV has good synergistic effect and better oil displacement effect. The physical simulation oil displacement experiment result shows that the oil displacement agent IV prepared by the surfactant composition for displacing oil of the high-temperature and high-salinity reservoir can embody high-efficiency oil displacement performance under the conditions of the high-temperature and high-salinity reservoir.
The invention has been described in detail with reference to specific embodiments and/or illustrative examples and the accompanying drawings, which, however, should not be construed as limiting the invention. Those skilled in the art will appreciate that various equivalent substitutions, modifications or improvements may be made to the technical solution of the present invention and its embodiments without departing from the spirit and scope of the present invention, which fall within the scope of the present invention. The scope of the invention is defined by the appended claims.
Claims (10)
1. A surfactant composition for a high-temperature high-salinity oil reservoir oil displacement agent is characterized by comprising a main agent and a synergist,
the main agent is fatty amine polyoxypropylene polyoxyethylene ether sulfonate, and a polyoxypropylene chain segment and a polyoxyethylene chain segment are introduced through fatty amine etherification;
the synergist is selected from quaternary ammonium salt, preferably one or more of alkyl trimethyl quaternary ammonium salt, Gemini quaternary ammonium salt and quaternary ammonium salt containing polyoxyethylene ether block.
2. The composition as claimed in claim 1, further comprising a cosolvent, wherein the cosolvent is selected from one or more of fatty alcohol polyoxyethylene polyglyceryl ether, fatty amine polyoxyethylene polyglyceryl ether, fatty alcohol polyoxypropylene polyoxyethylene polyglyceryl ether and fatty amine polyoxypropylene polyoxyethylene polyglyceryl ether.
3. The composition as claimed in claim 1, wherein the synergist is one or more of fatty alcohol polyoxyethylene glycidyl ether quaternary ammonium salts.
4. Composition according to one of claims 1 to 3,
the fatty amine polyoxypropylene polyoxyethylene ether sulfonate is prepared by etherifying, alkenylating and sulfonating fatty amine;
the fatty alcohol-polyoxyethylene ether reacts with halogenated propylene oxide in an alkali metal hydroxide aqueous solution in the presence of a phase transfer catalyst to obtain fatty alcohol-polyoxyethylene glycidyl ether, and trimethylamine and concentrated acid are added to react to obtain the fatty alcohol-polyoxyethylene glycidyl ether quaternary ammonium salt.
5. The composition of claim 2, wherein the cosolvent is prepared by a substitution reaction of a polyether and a halogenated propylene oxide to obtain a glycidyl ether intermediate containing an epoxy bond, and a ring-opening reaction of the glycidyl ether intermediate and polyglycerol.
6. Composition according to one of claims 1 to 3,
the main agent is fatty amine polyoxypropylene polyoxyethylene block polyether sulfonate, which has the following structure:
wherein R is alkyl or substituted aryl; m + n is more than or equal to 2 and less than or equal to 20, m is 2-20, and n is 2-20; i is 2-8; m, n and i are integers;
the fatty alcohol polyoxyethylene glycidyl ether quaternary ammonium salt has the following structure:
R0is alkyl or substituted aromatic radical(ii) a p is 2-20; p is an integer;
the cosolvent has the following structure:
wherein R is1Is alkyl or substituted aromatic; e is nitrogen or oxygen; a + b is more than or equal to 2 and less than or equal to 20; a is 0 to 20; b is 1 to 20; c is 2, 3 or 4; a. b and c are integers.
7. The composition as claimed in one of claims 1 to 3, wherein the mass ratio of the main agent to the synergist is 100 (1-16); the mass ratio of the main agent to the cosolvent is 100 (2-25).
8. The composition according to one of claims 1 to 3, wherein the surfactant composition for the oil displacement agent of the high-temperature and high-salinity reservoir is used in a solvent, and the solvent is selected from one or more of alcohol solvents and ether solvents,
preferably, the solvent further comprises water.
9. The composition according to claim 8, wherein the mass-to-volume ratio of the surfactant composition to the solvent for the oil displacement agent for the high-temperature and high-salinity oil reservoir is (1-20) g (100-150) mL.
10. The application of the surfactant composition for the oil displacement agent of the high-temperature and high-salinity oil reservoir is characterized in that the composition is used for crude oil displacement with the oil reservoir temperature higher than 70 ℃ and the mineralization degree higher than 15000 mg/L.
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| WO2023284178A1 (en) * | 2021-07-13 | 2023-01-19 | 黑龙江信维源化工有限公司 | Surfactant composition for oil displacement in high-temperature and high-minerality oil reservoirs |
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